Palladium-Catalyzed Highly Chemo- and Stereoselective Bisthiolation of Terminal Alkynes with Allyl Phenyl Sulfides via C-S Bond Cleavage.

Abstract

A facile and general method for palladium-catalyzed stereoselective bisthiolation of terminal alkynes with allyl phenyl sulfides has been developed. The scope and versatility of the reaction have been demonstrated, and a broad range of substrates bearing electron-donating and -withdrawing groups on the aromatic rings were all compatible with this reaction, providing the desired (Z)-1,2-dithio-1-alkenes in moderate to good yields. Preliminary mechanistic studies demonstrated that the sulfur source of the desired products may be successively incorporated into alkynes via C-S bond cleavage of two molecules of allyl phenyl sulfides and ruled out the possibility of vinyl sulfides, alkynyl sulfides, and disulfide intermediates being involved in this reaction.